Peroxy compounds and processes for their preparation

ABSTRACT

Peroxy compounds having the structural unit:   ARE USEFUL FOR THE PRODUCTION OF MONOMERS SUCH AS CAPROLACTAM WHICH IN TURN MAY BE POLYMERIZED TO GIVE USEFUL POLYMERS SUCH AS Nylon 6.

United States Patent Hawkins June 24, 1975 PEROXY COMPOUNDS ANDPROCESSES (56] References Cited FOR THEIR PREPARATION OTHER PUBLICATIONSInventor: Edwin George Edward H CA 15, 24l6-l7, (1921), Girsewald et21!.

Lower Kingswood, England [73] Assignee: BP Chemicals (U.K.) Limited, yExaminer-Donald Daus E l d Assismm Examiner-Raymond V. Rush I22] Filed:July 10, 1967 ABSTRACT [2]] Appl' 651969 Peroxy compounds having thestructural unit:

[30] Foreign Application Priority Data N H July 13, I966 United Kingdom3l380/66 Mar. 2, I967 United Kingdom 9963/67 C C Mar. 2 1967 UnitedKingdom 9973/67 May 20, 1967 United Kingdom 23546/67 00 May 20, 1967United Kingdom 23547/67 [52] US- (1-. 60/307 F; 260/2393 A; 60/ areuseful for the production of monomers such as 260/563 C; 260l583 260/5342 260/585 caprolactam which in turn may be polymerized to give R usefulpolymers such as Nylon 6. I51] Int. Cl C07d 85/06 158 Field 61 Search260/307 F. 563 R 50 Clam, N0

at elevated temperatures.

Examples of derivatives of dodecan-l,l2-dioic acid containing nitrogenbound to the 12 carbon atom are NH CO (Illa) decan-l ,lO-dicarbonimideHOOC(CH ,.CN

(llla) 1 l-cyano-undecanoic acid HOOC(CH ..,CONH

(lVa) l l-carbamoyl-undecanoic acid.

The starting material in the process, namely 1,1-peroxydicyclohexylamine is a white solid insoluble in water but solublein ethanol, which melts at 40 41 .5C and distills at 94 97C at apressure of 0.4 mm Hg and at l38l40C at a pressure of 12 mm Hg.

1 ,l -Dihydroxydicyclohexyl peroxide OH OH can be reacted with ammoniato give l,l'-peroxydicyclohexylamine.

EXAMPLE A To a stirred mixture of cyclohexanone (19.6 g) and ethanol (50cc.), kept at or below C, was added 1- amino-3,3.5-trimethylcyclohexylhydroperoxide (17.3 g, 78% pure); solution was complete in ca. min. Tothe solution was added conc. sulphuric acid (3 drops) and magnesiumsulphate and the mixture was stored at 0C for 3 days. The solid wasfiltered off, the filtrate washed with water, dried and distilled, togive cyclohexanone. dihydroisophorone and a fraction (1 1.5 g), b.p.90-100 at 0.02 mm Hg, peroxide equivalent 179. By mass spectroscopy theproduct was shownto contain the unsymmetrical peroxide Me Me and thesymmetrical peroxide 1,1 '-peroxydicyclohexylamine in the ratio 1:9.

EXAMPLE B Cyclohexanone (90 g), ammonia (50 c. water (20 cc. methanol(45 cc.) and E.D.T.A. l g) were stirred together and 30% hydrogenperoxide cc.) gradually added with the reaction temperature kept at 35.The mixture was stored at room temperature overnight, the productextract with ether, and the extract evaporated and the residue distilledto give cyclohexanone (22 g.) and a product which was identified asl,l-peroxy-dicyclohexylamine (64.4 g.), and leave a residue (2.0 g.).The peroxide distils at 94-97/0.4 mm, l38l40/l2 mm, and has a meltingpoint of 404l.5.

EXAMPLE C 1 The same conditions were used as in Example B except thatafter the periodof storage the bottom oily layer was separated,dissolved in ethanol. and the ethanolic solution added, with stirring,to water (2 litres). The 1,1'-peroxy-dicyclohexylamine separated assolid and filtered off. The yield of slightly wet product was 82 g.,redistillation giving 72.6 g of pure peroxide.

EXAMPLE D Cyclohexanone g), 0.880 ammonia (32 cc.), water (20 cc.),methanol (45 cc.) and E.D.T.A. (0.2 g) were stirred together and 30%hydrogen peroxide (70 cc.) gradually added with the reaction temperaturekept at -35". The mixture was stored at room temperature overnight, theoily layer separated, diluted with an equal volume of methanol and themethanolic solution added, with stirring, to cold water (2 litres).Solid was filtered off and on distillation gave the peroxide 1,1'-peroxy-dicyclohexylamine (71.5 g).

EXAMPLE E Cyclohexanone (90 g), 0.880 ammonia (50 cc.), water (20 cc.),methanol (45 cc.) and E.D.T.A. (1.0 g) were stirred together, and 30%hydrogen peroxide (70 cc.), added, with the reaction temperature kept at35. The temperature was kept at 35 for 4 hours and gaseous ammoniaslowly passed into the solution. The mixture was stored overnight atroom temperature; the peroxide crystallized out from the solution onaddition of water and was filtered off. Distillation gave cyclohexanone(3.5 g) and l,l'-peroxy-dicyclohexylamine (77.8 g). The aqueous phasewas extracted with ether and provided cyclohexanone (4.8 g) and noperoxide.

EXAMPLE F l ,1 'Dihydroxydicyclohexyl peroxide (26.5 g), 0.880 ammonia12.5 cc). water (35 cc.), methanol (12 cc.) and E.D.T.A. (0.2 g) werestirred together until the solid peroxide had dissolved and the mixtureleft at room temperature overnight. The product was extracted with etherand the ethered extract on distillation, gave cyclohexanone 1 g) and1.1-peroxydicyclohexylamine 17.6 g).

The l .1 -peroxydicyclohexyIamine may also be made by reacting theautoxidate of cyclohexanol i.e. the product of oxidation of cyclohexanolwith molecular oxygen. with ammonia.

EXAMPLE G l-Aminocyclohexyl hydroperoxide (13.1 g), cyclohexanone (9.8g), methanol (25 cc.) and ammonium acetate (1.0 g) were mixed and storedat overnight. Next day the product was diluted with water. extractedwith ether and the ethereal extract distilled to give unreactedcyclohexanone and 1.1-peroxydicyclohexylamine (12.5 g), whichrecrystallized from petrol had m.p. 39.540.5. underpressed on admixturewith authentic peroxide.

EXAMPLE H l-Aminocyclohexyl hydroperoxide 13.1 g). dihydroisophorone (14g). methanol (25 cc.) and ammonium acetate 1.0 g) were mixed, store at0C overnight and worked up as in the previous example. Distillation gavecyclohexanone and dihydroisophorone (9.0 g). an intermediate fraction(3.2 g). b.p. below l00C/0.7 mm. Hg, a fraction (8.1 g), b.p.110-1l4/0.7 mm of 3.3 .5 '-trimethyl-1 .1 '-peroxy-dicyclohexylamine(peroxide equivalent. 234; perchloric acid equivalent. 245; and residue(1.5 g). The process may be carried out in the liquid or gas phase. butis preferably carried out in the gas phase as the liquid phase reactiontends to give a complex mixture of products of which only part are thedesired derivatives of 1.12-dodecanedioic acid. The elevated temperatureto which the 1.1 '-peroxydicyclohexylamine is heated is suitably in therange 300C to 600C. and preferably from 400C to 600C. If the reaction isto be carried out in the gas phase it is preferred to use reducedpressures. Suitable pressures are of the order of to 250 mm Hg.

The vapour phase reaction may be carried out in any suitable manner. forexample by feeding a solution of the peroxyamine into the top of aheated column. which may be packed with inert material e.g. glass ballsand withdrawing the product containing the desired derivatives from thebase. The pyrolysis is carried out in an atmosphere of an inert gas.e.g. nitrogen. Any solvent which is inert to the conditions of thermalpyrolysis may be used for dissolving the peroxide e.g. ethanol.pyridine. B-picoline, benzene. chloroform. aqueous ethanol.cyclohexanone. tributylamine. ethylene glycol. The solution may be ofany desired concentration and suitably of 50 10% peroxide in solvent.The peroxide may also be fed as a vapour without solvent e.g. in astream of inert gas.

The nature of the derivative of l.l2-dodecanedioic acid obtained by theprocess will depend on the conditions used. If the reaction is carriedout in the vapor phase. the main products formed are decane-1.10-dicarbonimide (Ila). 1 l-cyano-undecanoic acid (Illa). 1l-carbomoyl-undecanoic acid (lVa). These three compounds are all whitesolids at room temperature. the imide (Ila) melting at 134- 136C. thenitrile-acid (llla) at 55 58C and the acid-amide (lVc) at 132 134C. Themain products formed are the imide (Ila) and the nitrile-acid (llla) andthe proportions in which these two compounds are found in the productare dependent on the temperature to which the starting material (la) isheated and the time for which it is maintained at that temperature. Hightemperatures and prolonged heating favour the formation of thenitrile-acid (Illa) while the formation of the imide (Ila) is favouredby lower temperatures and shorter periods of heating. Thus. in thevapour phase reaction at 15 mm Hg at bath temperatures in the range 375440C the main constituent of the product was the imide (Ila) while attemperatures in the range 470 510C the main constituent was thenitrile-acid (Illa). At a given temperature the proportion ofnitrile-acid is increased by increasing the pressure at which thethermal decomposition is carried out, by decreasing the rate of feed tothe heated column or by increasing the concentration of peroxide in thesolvent, i.e. by increasing the contact time.

The imide (Ila) and nitrile-acid (Illa) may suitably be separated fromthe crude product obtained by heating the peroxyamine (la) in the vapourphase by dissolving the crude product in petrol, i.e. a light petroleumfraction boiling in the range 40 60C and crystallizing the imide (Ila)or nitrile-acid (llla) by cooling or by distillation.

In addition to the C,- compounds described above. the thermaldecomposition of the 1,1 'peroxydicyclohexylamine yields smaller amountsof caprolactam and cyclohexanone. and other compounds.

The following examples in which all temperatures are in Celsius degreesand all pressures in millimetres of mercury illustrate the process.

EXAMPLE 1 The peroxide (la) (32 g.). dissolved in a mixture of ethanolcc) and pyridine (4 cc). was fed dropwise during 3 hours into a 14 inchlong glass tube half filled with glass balls and heated by a furnace toa temperature of 500 (at middle point). The pressure inside the reactionsystem was 150 mm and the pyrolysis was car ried out in a slow stream ofnitrogen. The product was condensed, the solvent removed and the residuedistilled to give three fractions and a residue (0.9 g). The firstfraction (2.8 g) was largely cyclohexanone but contained some pyridine;the second fraction (5.6 g) was mainly caprolactam; the third fraction(20.0 g) solidified and consisted mainly of ll-cyanoundecanoic acid(92.2% by titration).

EXAMPLE 2 The peroxide (Ia) 16 g.) dissolved in B-picoline (25 g) wasfed into the reactor used in Example I through which a slow stream ofnitrogen was passed. at a temperature and pressure of 500 and 150 mmrespectively during minutes. Distillation provided cyclohexanone. 21caprolactan fraction (3.1 g). a fraction (9.1 g) consisting largely of ll-cyanoundecanoic acid (88.5% by titration) and residue (0.7 g.).

EXAMPLE 3 The peroxide (la) (8g). dissolved in ethanol (40 cc) andpyridine 1 cc). was fed to the reactor used in Example I through which aslow stream of nitrogen was passed at a temperature and pressure of 590and 15 mm respectively, during 60 minutes. Distillation gave a fraction1.2 g) containing 50% caprolactam together with unreacted peroxide. anda fraction (5.0 g.) containing 87% lI-cyanoundecanoic acid together withcaprolactam and imide (Ila). as well as residue (0.4 g).

EXAMPLE 4 The peroxide (l) (8 g) dissolved in ethanol (40 cc) andpyridine 1 cc) was fed to the reactor used in Example 1 through which aslow stream of nitrogen was passed at a temperature and pressure of 500and 150 mm. respectively during 30 minutes. Distillation gave acaprolactam fraction (0.8 g). a fraction (5.7 g) containing ll-cyanoundecanoic acid (82% by titration) as well as caprolactam. and aresidue (0.3 g.).

EXAMPLE 5 The peroxide (Ia) (8g) dissolved in ethanol cc) and pyridinelcc) was fed at a temperature and pressure of 500 and 150 mmrespectively during 60 minutes into the reactor used in Example 1through which a slow stream of nitrogen was passed. Distillation gave acaprolactam fraction (0.9 g). a fraction (5.4 g) containing ll-cyanoundecanoic acid (86 by titration), and residue (0.3 g).

EXAMPLE 6 The peroxide (la) (8 g). dissolved in ethanol (40 cc) andpyridine 1 cc), was fed into the reactor used in Example through which aslow stream of nitrogen was passed at a temperature and pressure of 400and 150 mm respectively during minutes. Distillation gave a caprolactamfraction (0.8 g). a fraction (5.5 g) containing ll-cyanoundecanoic acid(40% by titration) and imide (Ila) and a residue (0.4 g).

EXAMPLE 7 The peroxide (la) (10 g), dissolved in chloroform (20 cc) wasfed to the reactor used in Example 1 through which a slow stream ofnitrogen was passed at a temperature and pressure of 440 and 15 mmrespectively during minutes. Solvent was evaporated from the product.the residue treated with petrol. the solution cooled and imide (5.6 g)filtered off. The filtrate was evaporated and residue distilled to givecyclohexanone (0.7 g). a caprolactan fraction (0.9 g), and a fraction1.6 g) containing mainly l l-cyanoundecanoic acid with some 1l-carbamoylundecanoic acid (lVa).

EXAMPLE 8 Peroxide (la) (8 g) dissolved in pyridine (20 cc) and water 10cc), was fed into the reactor used in Example 1 through which a slowstream of nitrogen was passed at a temperature and pressure of 510 and15 mm respectively during 45 minutes. The product was dissolved inchloroform and dried with anhydrous magnesium sulphate. The solvent wasevaporated and the residue mixed with petrol and cooled to yield 1lcyanoundecanoic acid (4.2 g). The filtrate was distilled to give afraction (0.8 g), consisting mainly of caprolactam, and a fraction 1.0g), largely the nitrile-acid (Illa).

EXAMPLE 9 Peroxide (la) (8 g) dissolved in cyclohexanone (20 g) was fedinto the reactor used in Example l through which a slow stream ofnitrogen was passed at a temperature and pressure of 440 and 15 mmrespectively, during minutes. The cyclohexanone was removed underreduced pressure and the residue treated with petrol and cooled to yieldslightly impure imide (2.6 g). Distillation of the filtrate gave acaprolactam fraction (0.6 g) and a fraction (3.2 g), containing imide(Ila). cyanoundecanoic acid (Illa) and carbamoylundecanoic acid (lVa).

EXAMPLE l0 Peroxide (la) (8 g) dissolved in a mixture of ethylene glycol(20 g) and ethanol (8 cc) was fed into the reactor used in Example 1through which a slow stream of nitrogen was passed at a temperature andpressure of 440 and 15 mm. respectively during 40 minutes. The productwas diluted with chloroform, washed with water to remove glycol andethanol, the chloroform solution evaporated and petrol added to theresidue. Cooling led to the separation of imide (4.0 g) and the filtratewas distilled to give cyclohexanone (0.7 g), a caprolactam fraction (0.5g) and a fraction l .3 g) containing the imide (Ila). nitrile-acid(Illa) and amideacid (lVa).

EXAMPLE 1 l The imide (Ila) (3 g) dissolved in pyridine (10 cc) was fedinto the reactor used in Example 1 through which a slow stream ofnitrogen was passed at a temperature and pressure of 510 and 15 mmrespectively during 45 minutes. From the product were isolated unreactedimide (1.6 g) and ll-cyanoundecanoic acid (1.1 g).

Caprolactam may be polymerized to give useful polymers viz nylon-6.

A process for the production of caprolactam comprises reactingl.1-peroxydicyclohexylamine with an alkali metal alkoxide.

l,1-Peroxydicyc1ohexylamine is produced as hereinbefore described.l.1'-Peroxydicyclohexylamine has the structure The alkali metal alkoxidemay be an alkoxide of any of the alkali metals, e.g. lithium, sodium orpotassium. Sodium is particularly preferred. The alkoxide is suitably alower alkoxide e.g. ethoxide or methoxide. methoxides being preferred.The poroxyamine and the alkoxide may be reacted together in solution ina solvent such as aromatic hydrocarbons e.g. benzene, and alkanols e.g.ethanol or methanol. Solvents of high dielectric constant lead to highrates of reaction although the yield of caprolactam may be reduced. Thepreferred solvents are alkanols. preferably the alkanol corresponding tothe alkoxide. thus when using a methoxide the reactants are preferablydissolved in methanol and when using an ethoxide the reactants arepreferably dissolved in ethanol.

The ratio of the number of moles of alkoxide to the number of moles of1,1'peroxydicyclohexylamine is suitably greater than 1:1. When thereaction is being carried out in solution the concentration of thereactants may vary within moderately wide limits.

The reaction is suitably carried out at moderately elevatedtemperatures. Thus temperatures up to 140C may be used, preferablytemperatures up to C.

The duration of the reaction will vary with the temperature used. thereaction being complete when no 7 8 more peroxide can be detected in thereaction mixture. (2.3 g), a caprolactam fraction (3.7 g). a higherboiling The presence of unreacted peroxide may be detected fraction (2.4g) and residue (0.7 g). The caprolactam by reacting the reaction mixturewith a known quantity fra tion contained 70% by weight of caprolactam byof potassium iodide in acetic acid. Any peroxide presi fl dspectroscopy, ent liberates iodine which can be estimated by titration 5with sodium thiosulphate. Suitable times are in the EXAMPLE 14 range 0.5to 10 hours.

The reaction can be carried out at sub-atmospheric Sodium 12 g) wasdissolved i h l 50 d and super-atmospheric pressure as well as atatmoperoxide 1 g) i ethano| 40 cc) d T p pressure- The reaction y becarried out 10 sulting solution was refluxed for 4 hours, the bulk ofthe under conditions such that the solvent is able to reflux ethanolremoved on h water pump d h id when heated Sufi'Kiiently and the P maybe treated as in Example I 1. There were obtained cyclosuch that thesolvent used to dissolve the reactants rehexanone 2 g) caprolactam f ti4 fluxes at the reaction tembbl'awre helping maintaining 76% by weightof caprolactam, a higher-boiling lain the reaction temperature cbnslam-5 fraction (1.2 g) containing l5% caprolactam, and

The caprolactam is recovered from the reaction mixa residue 5 ture inany suitable manner for instance by diluting the reaction mixture withwater followed by extraction of EXAMPLE the mixture with a liquid whichis immiscible with water and is a solvent for caprolactam. Suitableliquids are aromatic compounds, e.g. benzene. xylene. and chlorinatedhydrocarbons, especially the chlorinated lower aliphatic hydrocarbons,e.g. methylene chloride, chloroform. dichloroethane. Ethers, e.g.diethyl ether may also be used. Acid may optionally be added to thereactaining 83% caprolactam. by weight, and a residue (05 tion mlxtureafter addition of water. The quantity of acid is suitably such as tomake the reaction mixture just acid to Congo red indicator. The solventused to EXAMPLE l6 dissolve the reactants may be removed before thedilution with water ifdesired. The liquid used to extract the Lithium(0.8 g) dissolved in methanol cc) and Potassium (3.4 g) dissolved inmethanol (30 cc) was treated with the peroxide (lb) (10 g) in methanol(l0 cc) and the mixture refluxed for 2 hours. The reaction mixture wastreated as in Example ll and gave cyclohexanone (3.6 g). a caprolactamfraction (3.8 g) concaprolactam is then distilled from the extract toleave peroxide (lb) (10 g) in methanol ([0 cc were mixed the caprolactamand cyclohexanone, which may be and refluxed for l0 /z hours. Thereaction mixture was separated by e.g. distillation. treated as inExample 1 and gave cyclohexanone (3.8

By using the process high yields of caprolactam and g), a caprolactamfraction, (2.7 g), containing 59% cyclohexanone are obtained, based onthe equation: 35 caprolactam by weight, a higher-boiling fraction (1.0

NH Alkali metal =0 CH -CH -CH -CO Alkoxide 2 2 2 oo Gri -CH NH (1b)(11b) ([IIb) T following Examples in which all temperatures g)containing 30% caprolactam by weight. and residue are in celsius degreesand all pressures in millimeters of (0,5 mercury illustrate thisprocess. EXAMPLE 17 EXAMPLE 1 1 Sodium (2 g) was dissolved in methanol(25 cc) and Sodium (2g) was dissolved in methanol (30 cc) and Peroxidegl dd d, the mixture was refluxed h id (1b) 10 di l d i h l 10 for 1hour. The reaction product was then diluted with The mixture was heatedunder reflux for water, and then extracted With chloroform without hourswhen no peroxide remained. Water (ca. 30 cc) acidification to givecyblbbexanone a caprolacwas added to the reaction mixture and thesolution fTaCIiOIt g) Containing 65% caprolactam y made just acid toCongo red with hydrochloric acid; exwelgbi' blgber'bbibng. fraction ELCOnlaifliflg traction with chloroform followed by evaporation of 37%caprolactam by Welght and a residue g)- the solvent and distillation at15 mm. gave cyclohexab b may be polymerized to give useful P ynone (4.7g) and a caprolactam fraction (4.2 g) conmars for Instance "y taining93% by weight of caprolactam (by infra-red p b the b b of caprolactflm 9spectroscopyy prises bringing l.l -peroxyd1cyclohexylamine into contactwith an alkali metal hydroxide and an alkanol.

l,l '-Peroxydicyclohexylamine is produced as hereinbefore described. 1,1'-Peroxydicyclohexylamine has the structure EXAMPLE I2 As in Example I lbut at the end of the reflux period the bulk of the methanol wasevaporated at 15 mm Hg. the residue diluted with water, neutralised withacid and extracted with chloroform. Distillation gave cyclohexanone (4.]g) and a caprolactam fraction (4.5 g). ,5 87% pure by infra-redspectroscopy.

EXAMPLE l3 As in Example I l but replacing methanol by ethanol. heatingtime hour. Distillation gave cyclohexaone The alkali metal hydroxide maybe a hydroxide of any of the alkali metals, e.g. lithium. sodium orpotassium. Sodium hydroxide is particularly preferred.

Examples of suitable alkanols are the lower alkanols. e.g. methanol,ethanol and butanol. The quantity of alkanol used is preferably inexcess of 1 mole of alkanol per mole of alkali metal hydroxide.Preferably the quantity of alkanol is such that both the alkali metalhydroxide and peroxyamine are dissolved. The peroxide and hydroxide arepreferably brought into contact in the absence of added water. e.g. insolution in a substantially anhydrous alkanol. It may be advantageous tocarry out the reaction in the presence of a drying agent e.g. CaO, MgSOThe ratio of the number of moles of hydroxide to the number of moles ofl,l'peroxydicyclohexylamine is suitably greater than 1:]. When thereaction is being carried out in solution the concentration of thereactants may vary within moderately wide limits.

The reaction is suitably carried out at moderately elevatedtemperatures. Thus temperatures of 40 to l40C may be used. preferablytemperatures of 50 to 100C.

The duration of the reaction will vary with the temperature used, thereaction being complete when no more peroxide can be detected in thereaction mixture. The presence of unreacted peroxide may be detected byreacting the reaction mixture with a known quantity of potassium iodidein acetic acid. Any peroxide present liberates iodine which can beestimated by titration with sodium thiosulphate. Suitable times are inthe range 0.5 to 10 hours.

The reaction can be carried out at sub-atmospheric and super-atmosphericpressure as well as at atmospheric pressure. The reaction may be carriedout under conditions such that the solvent is able to reflux when heatedsufficiently and the pressure may then be such that the solvent used todissolve the reactants refluxes at the reaction temperature so helpingto maintain the reaction temperature constant. Cyclohexanone is producedas a by-product.

The caprolactam is recovered from the reaction mixture in any suitablemanner for instance by diluting the reaction mixture with water followedby extraction of the mixture with a liquid which is immiscible withwater and is a solvent for caprolactam. Suitable liquids are aromaticcompounds e.g. benzene, xylene, and chlorinated hydrocarbons, especiallythe chlorinated lower aliphatic hydrocarbons. e.g. methylene chloride,chloroform. dichloroethane. Ethers, e.g. diethyl ether may also be used.Acid may optionally be added to the reaction mixture after addition ofwater. The quantity of acid is suitably such as to make the reactionmixture just acid to Congo red indicator. The solvent used to dissolvethe reactants may be removed before the dilution with water if desired.The liquid used to extract the caprolactam is then distilled from theextract to leave the caprolactam and cyclohexanone. which may beseparated by e.g. distillation.

By using the process high yields of caprolactam and cyclohexanone areobtained, based on the equation:

NH Alkali metal Hydroxide (Ib) (K CH -CH -GH The following Examples inwhich all temperatures are in celcius degrees and all pressures inmillimetres of mercury illustrate the process.

EXAMPLE 18 Sodium hydroxide (3.5 g) was heated with methanol (30 cc) andperoxide [0 g) dissolved in methanol 10 cc) was added and the mixtureheated to reflux for 2 V: hours. After heating the solution was dilutedwith water and extracted with chloroform. Distillation gave acyclohexanone fraction (4.0 g). a caprolactam fraction (4.4 g)(containing 75% lactam by l.R.), and residue (0.] g.).

EXAMPLE 19 The same reactants were used as in Example 18 with theaddition of magnesium sulphate monohydrate (1.5 g) to the refluxingsolution. Heating was continued for 5% hours. Treatment of the reactionmixture as in Example l8 gave a cyclohexanone fraction (2.8 g). acaprolactam fraction (4.] g containing 8l% lactam by IR) and residue(0.2 g). Further caprolactam (0.2 g) was obtained by acidification ofthe aqueous phase followed by extraction with chloroform.

EXAMPLE 20 The same reactants were used as in Example [8 with theaddition of calcium oxide (2g) to the refluxing solution. Heating wascontinued for 2% hours. Treatment of the reaction mixture as in Examplel8 gave a cyclohexanone fraction (3.7 g). a caprolactam fraction (4.2 g;containing 85% lactam by IR.) and residue (0.2 g).

EXAMPLE 2] The same reactants were used as in Example 18 with theaddition of water (20c) to the refluxing solution. Heating was continuedfor 3 hours. Treatment of the reaction mixture as in Example l3 gave acyclohexanone fraction (3.3 g), a caprolactam fraction (4.5 g;containing lactam by LR.) and residue (0.2 g).

EXAMPLE 22 Potassium hydroxide (4.9 g), methanol (40 cc) and peroxide l0g) were heated under reflux for 2% hours. Treatment of the reactionmixture as in Example 18 gave a cyclohexanone fraction (L9 g) acaprolactam fraction (4.4 g; containing 80% lactam by LR). and ahigher-boiling fraction (0.4 g; containing 55% lactam by [.R.).

EXAMPLE 23 Sodium hydroxide (3.5 g), ethanol cc) and peroxide (l0 g)were heated under reflux for 2% hours. Treatment of the reaction mixtureas in Example 18 gave a low-boiling fraction 1.7 g), a caprolactamfraction (4.2 g; containing lactam by LR.) a higherboiling fraction (0.9g) and residue (0.4 g).

EXAMPLE 24 Sodium hydroxide (3.5 g). ethanol (40 cc) and per oxide 10 g)were heated reflux for 1% hours. Treatment of the reaction mixture as inExample [8 gave a low-boiling fraction (3.2 g; largely cyclohexanol byl.R.). a caprolactam fraction (3.9 g; containing 60% CH -CH NH tillExamples of derivatives of dodecane-l.l2-dioic acid containing nitrogenbound to the 12 carbon atom are (Ila) decane-l IO-dicarbonimide HOOC(CH-)m-CN (Illa) l l-cyano-undecanoic acid HOOC (CHzhw-CONH (IV a) l1-carbomyl-undecanoic acid The starting material in the process, namelyl,l -peroxydicyclohexylamine is produced as hereinbefore discussed.

The compound (la) is photo-chemically decomposed by any of the knowntechniques of photo-chemical decomposition. The photo-chemicaldecomposition may be carried out by using ultraviolet light to irradiatethe starting material (la).

Examples of suitable wavelengths of ultra-violet light which may be usedare those in the range 3,600 A to L850 A, for instance those in therange 3.600 A to 3. l 00 A. An example of a suitable source ofultra-violet light is the mercury vapour discharge lamp, which may havefor example a quartz envelope to allow shorter wavelengths to betransmitted than is possible with glass envelopes. Other glasses, forinstance borosilicate glasses may, however, be used successfully insteadof quarts.

The temperature and critical at which the reaction is carried out arenot ciritical. Thus temperatures in the range 50 to 50C may be used butit is convenient to use temperatures close to ambient temperature. e.g.l030C, and atmospheric pressures. It may be advantageous to provide forcooling of the reaction mixture which is being photo-chemicallydecomposed. This may be done by e.g. circulating cooling fluid betweenthe the source of the radiation and the reaction mixture. The reactionis preferably carried out in the liquid phase and this may be done bydissolving the starting material (la) in a solvent. Examples of suitablesolvents are ethanol, pyridine, B-picoline, benzene. chloroform.cyclohexanone. tributylamine. ethylene glycol. The concentration of theperoxide (la) in the solvent may vary within moderately wide limits.Examples of suitable concentrations are those in the range 2 to 24%wt/volume (i.e. wt. of solute against volume ofsolvent). Suitableconcentrations within the above range are for instance those between 8and 24% wt/volume. It may be advantageous to add an initiator to thestarting material (la) to assist the photo-chemical decomposition.

The principal product of the process is the inside (Ila, but the nitrileacid (Illa and amide (Ila) may also be obtained. though generally insmaller quantities. Cyclohexanone and caprolactam are also produced inthe process of the present invention and may be recovered.

The imide (Ila) may be recovered from the reaction product by anysuitable means for instance by dissolving the crude product in 4060Cpetrol (a light petroleum distillate substantially free of aromatics andboiling in the range 40-60C at atmospheric pressure), and crystallizingthe imide (lla from the solution in petrol.

The process is further illustrated by the following examples.

EXAMPLE 25 The apparatus used consisted of a tubular U.V. source.consisting of a mercury vapour discharge lamp surrounded by twoconcentric tubes or borosilicate glass. The tube next adjacent to thelamp carried a stream of water, which cooled a solution of l .l'-peroxydicyclohexylamine (la) (5g) in benzene [30 cc), located in thespace between the tube next adjacent to the lamp and the tube nextoutwards from the lamp. The solution of the starting material (la) waskept mixed by a stream of nitrogen bubbles fed into the solution from asintered glass disc sealed into the base of the tube surrounding thereaction mixture.

The solution of the starting material (la) was irradiated by the lampfor [0 hours and the solvent was then removed by evaporation underreduced pressure. The residue was mixed with 40- 60C petrol (i.e. lightpetroleum distillate substantially free of aromatics and boiling in therange 40 to 60C at atmospheric pressure) to precipitate the imide (Ila).

The imide precipitated as above was filtered off and re-crystallizedfrom ethanol and the filtrate remaining after removal of the precipitatewas separated by distillation into fractions. The products obtained were(a) l.3 g. of solid imide (Ila) (m.p. l32 l34C) (b) 0.8 g. ofa fractionboiling in the range 1 20- 160C at 14 mm Hg. and containing 30% by wt.caprolactam. (c) 0.8 g. of a fraction boiling in the range l60 230C andl4 mm Hg and containing l5% by wt. caprolactam together with quantitiesof imide (lla) and (d) 0.4 g. of residue.

EXAMPLE 26 The same reactants and conditions were used as in Example 25except that IS g. of peroxide (la were used and irradiation with thelamp was continued for 22 hours. The products obtained were (a) 4.2 g.of solid imide (lla). (b) 0.7 g. of a distillate fraction consisting ofcyclohexanonc. (c) l .7 g. of a fraction boiling in the range l35 I60Cat 15 mm Hg and containing by wt. of caprolactam, (d) 4.4 g. of afraction boiling in the range l60 235C at 15 mm Hg and containing about20% by wt. of caprolactam together with other amides. (e) l .4 g. ofafraction boiling in the range 238 285C at 15 mm Hg and containing imide(lla) and (f) 0.9 g. of residue.

EXAMPLE 27 The same reactants and conditions as in Example 26 were usedexcept that benzophenone 1.0 g.) was present with the peroxide (la) andthe solution was irradiated for 24 hours. The products obtained were (a)3.7 g. of solid imide (11a). (c) 0.6 g. ofcyclohexanone dis tillatefraction (c) 1.6 g. of a fraction boiling in the range 100C to 180C at14 mm Hg, containing 55% by weight of caprolactam, (d) 4.4 g. of afraction boiling in the range 180 290C at 14 mm Hg containing secondaryamides. (e) and 2.1 g. of residue.

EXAMPLE 28 The same conditions were used as in Example 27 butZ-methylanthraquinone (0.2 g.) was used in place of benzophenone. andirradiation with the lamp was carried out for 25 hours. The productsobtained were (a) 4.3 g. of the solid imide (lla). (b) 0.3 g. ofcyclohexanone, (c) 1.8 g. of a fraction boiling in the range 130 to 170Cat 15 mm Hg containing 48% by wt. of caprolactam. (d) 4.5 g. of afraction boiling in the range 170 to 270C at 15 mm Hg. (e) and 1.6 g. ofresidue.

EXAMPLE 29 The same conditions were used as in Example 26 except thatthe benzene was replaced by ethanol 125 cc) and irradiation with thelamp was carried out for 19 hours. The products obtained were (a) 4.0 g.of solid imide (11). (b) 0.6 g. of cyclohexanone, (c) 3.2 g. of afraction boiling in the range 135 to 160C at 15 mm Hg and containing 40%by wt. of caprolactam, (d) 3.9 g. of a fraction boilin in the range 160245 at 15 mm Hg. containing amides. and (e) 1.3 g. of residue.

EXAMPLE 30 The same conditions as Example 26 were used except that thebenzene was replaced by pyridine 125 cc) and irradiation with the lampwas carried cut for 29 hour. The products were (a) 4.0 g. of solid imide(lla). (b) 0.7 g. of cyclohexanone, (c) 3.5 g. of a fraction boiling inthe range 130 to 170C at 15 mm Hg, containing caprolactam. (d) 3.5 g. ofa fraction boiling in the range 170 to 245C at 15 mm Hg containing alinear secondary amide and 1.3 g of residue.

Caprolactam may be polymerized to give useful polymers viz. nylon-6.

A process for the production of caprolactam comprises reacting1.1'-peroxydicyclohexylamine with an alkali metal alkoxide or aroxide.

1,1'-Peroxydicyclohexylamine is produced as hereinbefore described.1.1-Peroxydicyclohexylamine has the structure;

The term aroxides" as used herein means compounds formed by thereplacement of hydrogen by a metal in a hydroxy group linked directly toan aromatic nucleus. An example of a suitable aroxide is sodiumphenoxide but other phenoxides including phenoxides with substituentsother than hydroxy groups may be used. Aroxides derived from compoundshaving more than one hydroxy group linked to the aromatic nucleus may beused. The preferred aroxides are those derived from the benzene nucleus.

The alkali metal alkoxide or aroxide may be an alk oxide or aroxide ofany of the alkali metals, e.g. lithium. sodium or potassium. Sodium isparticularly preferred. Examples of suitable alkoxides are the loweralkoxide. e.g. ethoxide or methoxide, methoxides being preferred.Butoxides. in particular n-butoxides are suitable and the use ofn-butoxides is particularly advantageous. as they can be isolated fromthe reaction of n-butanol and alkali metal hydroxides. The peroxyamineand the alkoxide or arocide may be reacted together in solution in asolvent such as aromatic hydrocarbons. e.g. benzene. phenols andalkanols, e.g. ethanol or methanol. Solvents of high dielectric constantlead to high rates of reaction although the yield of caprolactam may bereduced. The preferred solvents are alkanols and when an alkoxide isused. the alkanol is preferably the alkanol corresponding to thealkoxide. thus when using a methoxide the reactants are preferablydissolved in methanol and when using an ethoxide the reactants arepreferably dissolved in ethanol. However, when using higher alkoxidesand aroxides the lower alkanols are the most suitable solvents. Thus,when using an nbutoxide, or a phenoxide, the most satisfactory resultsare obtained if the reaction with 1.1' peroxydicyclohexylamine iscarried out in methanol.

Examples of suitable ratios of the number of moles of alkoxide oraroxide to the number of moles of 1.1 'peroxydicyclohexylamine are thosegreater than 1:1. When the reaction is being carried out in solution theconcentration of the reactants may vary within moderately wide limits.

The reaction is suitably carried out at moderately elevatedtemperatures. Thus. temperatures of 40 to 140C may be used, preferablytemperatures of 50 to 100C.

The duration of the reaction will vary with the temperature used, thereaction being complete when no more peroxide can be detected in thereaction mixture. The presence of unreacted peroxide may be detected byreacting the reaction mixture with a known quantity of potassium iodidein acetic acid. Any peroxide present liberates iodine which can beestimated by titration with sodium thiosulphate. Suitable times are inthe range 0.5 to hours.

The reaction can be carried out at sub-atmospheric and super-atmosphericpressure as well as at atmospheric pressure. The reaction may be carriedout under conditions such that the solvent is able to reflux when heatedsufficiently and the pressure may then be such that the solvent used todissolve the reactants refluxes at the reaction temperature so helpingto maintain the reaction temperature constant.

The caprolactam is recovered from the reaction mixture in any suitablemanner for instance by diluting the reaction mixture with water followedby extraction of the mixture with a liquid which is immiscible withwater and is a solvent for caprolactam. Examples of suitable liquids arearomatic compounds, e.g. benzene. xylene. and chlorinated hydrocarbons.especially the chlorinated lower aliphatic hydrocarbons. e.g. methylenechlo- 3 ,89 l ,663 1 S 16 ride. chloroform. dichloroetharle. Ethers.e.g. diethyl taining 83% caprolactam. by weight. and a residue (0.5ether may also be used. Acid may optionally be added g). to the reactionmixture after addition of water. The quantity of acid is suitably suchas to make the reaction EXAMPLE 36 mixture just acid to Congo redindicator. The solvent 5 Lithium g) dissolved in methanol an used todissolve the reactants may be removed before peroxide (lb) (l0 g) inmethanol cc were mixed the dilution with water if desired. The liquidused to exand refluxed for 10% hours. The reaction mixture was tract thecaprolactam is then distilled from the extract treated as in Example Iand gave cyclohexanone (3.8 to leave the caprolactam and cyclohexanone.which g). a caprolactam fraction. (27 g). containing 59% may beseparated by e.g. distillation. l0 caprolactam by weight, ahigherboiling fraction (1.0 By using the process high yields ofcaprolactam and g) C ntaining 30% caprolactam by weight d ducyclohexanone are obtained. based on the equation: (0.5 g).

Alkali metal 2 2 2 Co 00 alkoxide CH2-crl2 1 fl (1],) (11b) The processwill now be illustrated by the following EXAMPLE 37 Examples in whichall temperatures are in celsius de- Sodium (2g) was dissolved inmethanol cc) and grees and all pressures lll mlllmeters of mercury.

peroxide (lb) (10 g) added. the mixture was refluxed EXAMPLE 3 for 1hour. The reaction product was then diluted with water, and thenextracted with chloroform without acidification to give cyclohexanone(2.9 g). a caprolactam fraction (4.8 g). containing 65% caprolactam byweight, a higher-boiling fraction (0.3 g), containing 37% caprolactam byweight and a residue (0.2 g).

Sodium (2 g) was dissolved in methanol cc) and 25 the peroxide (lb) l0g), dissolved in methanol 10 cc), added. The mixture was heated underreflux for 1 /2 hours when no peroxide remained. Water (ca. 30 cc) wasadded to the reaction mixture and the solution made just acid to Congored with hydrochloric acid; ex- 30 EXAMPLE 38 traction with chloroformfollowed by evaporation of the solvent and distillation at 15 mm. gavecyclohexanone (4.7 g) and a caprolactam fraction (4.2 g) containing 93%by weight of caprolactam (by infra-red spectroscopy).

Sodium n-butoxide (from 2 g of sodium) was dissolved in methanol (25cc), and the peroxide (lb) (10 g) in methanol 10 cc) added. The solutionwas heated under reflux from l /z hours; the methanol was evaporated offunder reduced pressure. water added to the EXAMPLE 2 residue and thesolution extracted with chloroform. Distillation gave a fractioncontaining n-butanol and cyclohexanone (2.2 g of the ketone byestimation with 40 hydroxylamine hydroochloride, a caprolactam fraction(5.] g, containing 87% lactam by LR.) and a residue As in Example 31 butat the end of the reflux period the bulk of the methanol was evaporatedat 15 mm Hg. the residue diluted with water, neutralised with acid andextracted with chloroform. Distillation gave cyclo- (0 3 g) hexanone(4.] g) and a caprolactam fraction (4.5 g). 87% pure by infra-redspectroscopy. EXAMPLE 39 EX MPL 33 Sodium phenoxide l 1.0 g) in methanol(30 cc) was mixed wiith peroxide (lb) (l0 g) in methanol (10 cc) andheated under reflux for 6% hoursfThe product was diluted with water. thesolution extracted with chloroform and the extract distilled to givecyclohexanone As in Example 31 but replacing methanol by ethanol.Heating time V2 hour. Distillation gave cyclohexanone (2.3g), acaprolactam fraction (3.7 g), a higher boiling fraction and resume 1 Thecaprolactam (1.8 g). a caprolactam fraction (4.3 g,) containing 70%fraction contalned 70% by weight of caprolactam by lactam y IR.) andresidue (015 g mfra'red spectroscopy The compounds described as aroxidesmay also be EXAMPLE 34 described as aryloxides but the slight differencein nomenclature does not affect the identity of the compound concerned.

A process for the production of derivatives of alkane a. -dioic acidshaving nitrogen bound to the w-carbon atom comprises heating a compoundof formula Sodium 1.2 g) was dissolved in ethanol (50 cc) and peroxide(lb) (10 g) in ethanol (40 cc) added. The resulting solution wasrefluxed for 4 hours, the bulk of the ethanol removed on the water pumpand the residue treated as in Example 31. There were obtainedcyclohexanone (2.5 g). caprolactam fraction (4.0 g) contain- A /NH A ing76% by weight of caprolactam, a higher-boiling L ,L (F) fraction 1.2 g)containing 10 15% caprolactam. and 00 a residue (0.5 g). where X and Xare divalent aliphatic radicals which may be the same or different. atelevated temperatures.

EXAMPLE 35 In radicals X. X the number of carbon atoms which Potassium(3.4 g) dissol n m thanol (30 cc) was are in the ring may for examplevary from 4 to l l. i.e.

treated with the peroxide (lb) l0 g) in methanol (10 there may bebetween 5 and l2 atoms in the ring. Ex-

cc) and the mixture refluxed for 2 hours. The reaction amples ofcompounds of formula (F) are those commixture was treated as in Example3l and gave cyclopounds where X is a radical having 4 to 6 carbon atomshexan n -6 g). a caprol ctam fractiOn g) conin the ring. Examples ofsuch compounds are and b) 2 R R1 2 R3 1 NH R5 M (a) l I 5 10 R5 l I 6 9s e where R. R' are alkyl groups or hydrogen.

The preferred compounds are those in which R, R is hydrogen or loweralkyl. e.g. methyl, ethyl, propyl.

Specific examples of compounds according to the present invention are:

l.l '-peroxy dicyclopentylamine which is a white solid with a meltingpoint of 22-23C.

4.4 '-dimethyl-l .l '-peroxydicyclohexylamine is a white solid withmelting point l l9-l2lC.

He NH Me I 00 E I Ma llle Ma 3.3.5.3 ',3 5' hexamethyl-l .l'-peroxydicyclohexylamine which boils at I C at a pressure of 2 mm. Hg.

which in these alkane-dioic acid derivatives, the chain having thecarboxy group or its derivative at either end will contain the samenumber of carbon atoms as the sum of the carbon atoms in the two rings.and this chain will carry substituents corresponding to the substituentson the two rings. Thus the nitrogen-containing alkane dioic acidderivatives prepared from a compound of formula (F) having an alkylsubstituent in each ring will have two alkyl substituents on the chaincontaining the carboxy groups or the derivatives of the carboxyl groupse.g. CONH CONHCO, or -CN.

Examples of derivatives of alkane-a.wdioic acids containing nitrogenbound to the w carbon atoms are Ni-l (ca p decan-l IO-dicarbonimideHOOC-(CH )...CN

(lllc) l 1-cyano-undecanoic acid HOOC(CH .,CONH

(lVc) l l-carbamoyl-undecanoic acid and derivatives of these compoundsin which the carbon chain carries alkyl substituents. e.g. ll-cyano-dimethylundecanoic acids.

The process may be carried out in the liquid or gas phase, but ispreferably carried out in the phase as the liquid phase reaction tendsto give a complex mixture of products of which only part are the desiredderivatives of alkano-a. -w-dioic acids. Examples of elevatedtemperatures to which the peroxyamine F is heated are those in the range300C to 600C and preferably from 400C to 600C. If the reaction is to becarried out in the gas phase it is preferred to use reduced pressures.Examples of suitable pressures are those of the order of 10 to 300 mm.Hg.

The vapour phase reaction may be carried out in any suitable manner, forexample by feeding a solution of the peroxyamine into the top of aheated column. which may be packed with inert material e.g. glass ballsand withdrawing the product containing the desired derivatives from thebase. The pyrolysis may be carried out in an atmosphere of an inert gas,e.g. nitrogen. Any solvent which is inert to the conditions of thepyrolysis reaction may be used for dissolving the peroxide. e.g.ethanol. pyridine, B-picoline. benzene, chloroform. aqueous ethanol,cyclohexanone, tributylamine. ethylene glycol. The solution may be ofany desired concentration for example 50-10% by weight peroxide insolvent. The peroxide may also be fed as a vapour without solvent, e.g.in a stream of inert gas.

The nature of the derivative of alkane-a. w-dioic acid obtained by theprocess of the present invention will depend on the conditions used. Ifthe reaction is carried out in the vapour phase the main products formedare derivatives of alkane-a.w-dicarbonimide nitrile acids. and amideacids. As an example if l.l -peroxydicyclohexylamine is heated in thevapour phase at elevated temperature. the dicarbonimide is decane-l.l0-

dicarbonimide (llc) the nitrile acid is l lcyanoundecanoic acid (lllc)and the acid-amide is l lcarbamoyl undecanoic acid (lVc). The skeletalstructure of the derivatives produced will depend upon the nature andposition of any substituents on the rings of the compound F fed to thereactor. The type of derivative produced will depend on the reactionconditions. High temperatures favour the formation of the nitrileacid orits alkyl substituted derivatives. At a given temperature the proportionof nitrile-acid or its derivatives is increased by increasing thepressure at which the thermal decomposition is carried out. bydecreasing the rate of feed to the heated column or by increasing theconcentration of peroxide in the solvent. i.e. by increasing the contacttime.

Examples of methods by which the derivative of alkane-a.w-dioic acid maybe separated from the crude product are distillation andrecrystallization from solvents.

The thermal decomposition of compounds of formula F in addition to thederivatives of dioic acid compounds referred to above also yieldslactams, cycloalkanones, which may be alkyl substituted depending uponthe nature of any substituents in compound F. The number of carbon atomsin the lactam rings will be the same as that in the rings of theperoxyamine F from which they were derived and any substituents on thecarbon atoms in the lactam ring will also correspond to those on thering of the peroxyamine from which the lactam was derived.

NH (G (1 M Ma Thus a compound of formula would give 4- methylcaprolactamand 4-methylcyclohexanone.

The process willl be illustrated by the following examples.

EXAMPLE 40 A peroxide was prepared by reacting together3-methylcyclohexanone. hydrogen peroxide. and am monia. This peroxidewas Me NH Me 1 together with isomers in which the methyl group is alsoseparated by a two carbon atoms in the chain from the carbon atom towhich the peroxy group is attached. The pereoxide (5 g.) was dissolvedin ethanol l 5 c.c.) and the solution dropped through a column (1.5 cm.internal diameter) containing 8 inches of glass beads and heated to 400;the pyrolysis was carried out at 150 mm. pressure in a slight stream ofnitrogen. Addition occupied hr. The product was distilled to give3-methylcyclohexanone (0.4 g.) a methylcaprolactam fraction (1.2 g.).and a fraction (2.6 g.). b.p. l90250/l4 mm.. shoen by [.R. and N.M.R.spectra to contain dimethyl-w-cyanoundecanoic acid isomers as well assome lactam and amide-acid. The cyano acids were extracted with base.and had b.p. 230240/l4 mm.; acid equivalent 238 (calc. 239).

EXAMPLE 4i A peroxide was prepared by reacting together4-methylcyclohexanone. hydrogen peroxide. and am monia. The resultingperoxide 4.4'-dimethyl-l.l peroxy dicyclohexylamine (5 g.) was dissolvedin ethanol (60 c.c.) and the solution dropped through the heated columnas in example 40 at 400ll50 mm. in 45 min. Part of the peroxide had notreacted. so that the product. after evaporation of the ethanol, wasredis solved in benzene (20 c.c.) and the solution dropped through thesame column in l hr. Distillation gave 4 -methylcyclohexanone (0.6 g.) a4-methylcaprolactam fraction (0.8 g.) and a fraction (1.8 g.). b.p.l240/ l 4 mm., shown by l.R. spectroscopic examination to contain theexpected dimethyl-wcyanoundecanoic acid as well as some amides and anunsaturated compound.

EXAMPLE 42 The peroxide 10 g.) from dihydroisophorone. hydrogen peroxideand ammonia was dissolved in ethanol 15 cc.) and the solution droppedthrough a heated column, as in example 40 at 500/l 50 mm. during /4 hr.Distillation of the product gave dihydroisophorone l .7 g. atrimethylcaprolactam fraction (2.4 g.). a fraction (L6 g.). b.p.l80-220/l5 mm. and a fraction (2.0 g.). b.p. 240246/l 5 mm. containingnitrile acids.

EXAMPLE 43 The peroxide 10 g.) from cyclopentanone. hydrogen peroxideand ammonia was dissolved in ethanol (l0 c.c.) and the solution droppedthrough a heated column as in example 40 at 500C/l 50 mm. Hg during hr.Distillation of the product gave cyclopentanone (0.1 g.) valeric acid(0.3 g.). a cyano-nonanoic acid fraction (7.8 g.) residue (0.5 g.). Thecyano acid had a melting point 50-52C on recrystallization.

Lactams may be polymerised to give useful products. e.g. caprolactam maybe polymerised to give nylon-6.

A process for the production of lactams comprises reacting compounds offormula:

where X, X are divalent aliphatic radicals which may be the same ordifferent. with an alkali metal alkoxide or aryloxide or a mixture of analkali metal hydroxide with an alkanol or a hydroxy-substituted arylcompound.

Compounds of formula (F) are produced as hereinbefore described. Inradicals X. X the number of carbon atoms which are in the ring may forexample vary from 4 to l l. i.e. the total number of carbon atoms in thering may be between 5 and l2. Examples of compounds of formula (F) arethose compounds where X is a radical having 4 to 6 carbon atoms in thering. Examples of such compounds are where R. R are alkyl groups orhydrogen.

The preferred compounds are those in which R. R is hydrogen or loweralkyl. e.g. methyl. ethyl. propyl.

Specific examples of compounds are:

NH O 1.1 '-peroxy dicyclopentylamine which is a white solid with amelting point of 2223C.

NH 6 (l Me Me 4.4'-dimethyl-l .l '-peroxydicyclohexylamine is a whitesolid with melting point 1 l9l2lC.

which Me NH Me Me Me Me Me which boils at l24l 26at a pressure of 0.4mm. Hg.

and

NH (F O 1,1 '-peroxydicycloheptylamine which boils in the range l-l30Cat a pressure of 0.8 mm. Hg.

These compounds may be made by the reaction of at least one cyclicketone of formula with hydrogen peroxide and ammonia. and can beconsidered. regardless of the method by which they are made. asderivatives of the cyclic ketones from which they could be formed.

The term aryloxides as used herein means compounds formed by thereplacement of hydrogen by a metal in a hydroxy group linked directly toan aromatic nucleus. An example of a suitable aroxide is sodiumphenoxide but other phenoxides including phenoxides with substituentsother than hydroxy groups may be used. The preferred aroxides are thosederived from the benzene nucleus. The term hydroxyaryl compounds" asused in this specification means the compounds in which the hydroxygroup is linked directly to an aromatic nucleus. Examples of suitablehydroxy-aryl compounds are those from which the aryloxides" referred toabove may be derived.

The alkali metal alkoxide. aryloxide or hydroxide may be an alkoxide,aryloxide or hydroxide of any of the alkali metals e.g. lithium, sodiumor potassium. Sodium is particularly preferred.

Examples of suitable alkoxides are the lower alkoxides. e.g. ethoxide ormethoxide. methoxides being preferred. Butoxides. in particularn-butoxides. are suitable and the use of n-butoxides is particularlyadvantageous. as they can be isolated from the reaction of nbutanol andalkali metal hydroxides. It is not necessary however to isolate thealkoxide which may be formed in situ in the reaction mixture. lf alkalimetal hydroxides are combined with alkanols and hydroxy-aryl compoundswith elimination of water. alkoxides or aryloxides will be produced, andthe mixtures of alkali metal hydroxides with alkanols or hydroxy-arylcompounds will often contain alkoxides or aryloxides in equilibrium withthe hydroxide. The presence of the water produced by the reaction of thealkanol or hydroxy aryl compound with the alkali metal hydroxide mayhowever give rise to sidereactions which do not take place when thereaction is carried out using alkoxides or aryloxides prepared bymethods which do not involve the production of water. Where mixtures ofalkali metal hydroxide and alkanols are used examples of suitablealkanols are the lower alkanols, e.g. methanol. ethanol and butanol. Thequantity of alkanol used is preferably in excess of 1 mole of alkanolper mole of alkali metal hydroxide. Preferably the quantity of alkanolis such that both the alkali metal hydroxide and peroxyamine aredissolved. The peroxide and hydroxide are preferably brought intocontact in the absence of added water. e.g. in solution in asubstantially anhydrous alkanol. It may be advantageous to carry out thereaction in the presence of a drying agent e.g. CaO. MgSO.. Theperoxyamine and the alkoxide or aryloxide may be reacted together insolution in a solvent such as aromatic hydrocarbons, e.g. benzene.phenols and/or alkanols. e.g. ethanol or methanol. Solvents of highdielectric constant lead to high rates of reaction although the yield oflactam may be reduced. The preferred solvents are alkanols and when analkoxide is used. the alkanol is preferably the alkanol corresponding tothe alkoxide. thus when using a methoxide the reactants are preferablydissolved in methanol and when using an ethoxide the reactants arepreferably dissolved in ethanol. However, when using higher alkoxidesand aryloxides the lower alkanols are the most suitable solvents. Thus.when using an n-butoxide. or a phenoxide. the most satisfactory resultsare obtained if the reaction with l.l' peroxydicyclohexylamine or otherperoxyamines is carried out in methanol.

Examples of suitable ratios of the number of moles of the alkali metalcompound (whether alkoxide. aryloxide or hydroxide) to the number ofmoles of peroxyamine are 0.2 to 2. When the reaction is being carriedout in solution the concentration of the reactants may vary withinmoderately wide limits.

The reaction can be carried out at moderately elevated temperatures.Examples of suitable temperatures are those in the range 40l 60C,preferably temperatures of 50 to lOC.

The duration of the reaction will vary with the temperature used, andthe alkoxide and peroxyamine concentrations, the reaction being completewhen no more peroxide can be detected in the reaction mixture. Thepresence of unreacted peroxide may be detected by reacting the reactionmixture with a known quantity of potassium iodide in acetic acid. Anyperoxide present liberates iodine which can be estimated by titrationwith sodium thiosulphate. Examples of suitable times are those in therange of ().l to hours.

The reaction may be carried out at sub-atmospheric and super-atmosphericpressure as well as at atmospheric pressure. The reaction may be carriedout under conditions such that the solvent is able to reflux when heatedsufficiently and the pressure may then be such that the solvent used todissolve the reactants refluxes at the reaction temperature, so helpingto maintain the reaction temperature constant.

The lactum is recovered from the reaction mixture in any suitable mannerfor instance by diluting the reaction mixture with water followed byextraction of the mixture with a liquid which is immisoible with waterand is a solvent for the lactam produced. Examples of suitable liquidsare aromatic compounds, e.g. benzene, xylene. and chlorinatedhydrocarbons especially the chlorinated lower aliphatic hydrocarbons.e.g. methylene chloride. chloroform. dichloroethane. Ethers, e.g.diethyl ether may also be used. Acid may optionally be added to thereaction mixture after addition of water. The quantity of acid issuitably such as to make the reaction mixture just acid to Congo redindicator. The solvent used to dissolve the reactants may be removedbefore the dilution with water if desired. The liquid used to extractthe lactam is then distilled from the extract to leave the lactam andcyclic ketone which may be separated by e.g. distillation.

Where X and X are the same. as when the peroxyamine F is formed fromonly one cyclic ketone, there will generally be two lactam isomersformed corresponding to introduction of nitrogen into the ring on eitherside of the carbon atom to which the peroxy group was attached, whichwill correspond to the carbon atom forming part of the carbonyl group inthe ketone of which the peroxy amine F is a derivative. Thus aperoxyamine which is a derivative of 3-methylcyclohexanone is decomposedby the process of the present invention to give 3-methyl caprolactam and5- methyl caprolactam lrle 0 Me I] I?" W EXAMPLE 44 The peroxide derivedfrom 3-methylcyclohexanone. hydrogen peroxide and ammonia Me NH [0 g.)was added to a solution of sodium methoxide in methanol (2 g. sodium in40 c.c. methanol), and the mixture heated under reflux for 2 hrs.; onlya small amount of peroxide remained unreacted. The solution was cooled,diluted with water, neutralised with hydrochloric acid and extractedwith chloroform. Distillation of the chloroform extract gave3-methylcyclohexanone (4.7 g.). methylcaprolactam (4.1 g.). b.p.l45l50/l5 mm., and residue (0.5g). Examination of the methylcaprolactamfraction of N.M.R. spectroscopy showed it to be a mixture of 3- and 5-methylcaprolactam; on storage this fraction crystallised and severalrecrystallisations yielded the 3- methylcaprolactam. rn.p. 97100.

EXAMPLE 45 The peroxide derived from 4-methylcyclohexanone. hydrogenperoxide and ammonia NH D Kl No Me was added to a solution of sodiummethoxide in methanol l g. of sodium in 20 cc. methanol) and the mixtureheated under reflux for 2 hr. when very little peroxide remainedunreacted. The product was worked up as in Example 44 to give, ondistillation, 4-methylcyclohexanone (2.2 g.). r-methylcaprolactam (2.2g.). b.p. l45-l50/l5mm., and residue (0.3 g.). The structure of thelactam was confirmed by IR. and N.M.R. spectra.

Me and isomers EXAMPLE 46 0 and isomeu Me NH M 5 I 00 l I M Me Me Me (75g.) was added to a solution of sodium methoxide in methanol 1.5 g. ofsodium in 30 cc. methanol) and the mixture heated under reflux for 2hr.when very little peroxide remained unreacted. The product was worked upas in Example 44 to give. on distillation, dihydroisophorone (4.] g.),trimethylcaprolactam (3.1 g.). and residue (0.l g.). The structure ofthe lactam was confirmed by IR. and N.M.R. spectra; the N.M.R. spectrumshowed that both Me Me gmo Me Me and were present. the latter being themajor component.

EXAMPLE 47 A wide range of atoms and groups may be attached to the freevalencies in the structure (1) Examples of groups which may be attachedto the free valencies in structure (l) are hydrogen, alkyl and arylgroups. One, or both, of the carbon atoms in structure (I) may form partof a ring or rings into which they are bonded by their free valencies.Examples of suitable rings are those containing from 5 to 7 carbon atomsor more in the ring, and this ring may be joined to other rings.

It is found that compounds in which one or more of the free valenciesare linked to hydrogen atoms may tend to be unstable and decompose. [ftherefore it is desired to store a compound of structure (I) for anylength of time it should preferably not contain any hydrogen atoms boundto the free valencies.

Where neither of the carbon atoms in structure (I) forms part ofa ring,it is preferred that at least one alkyl group be bonded to each carbonatom in the structure (I) the two remaining free valencies in structure(I) being satisfied by hydrogen. alkyl or aryl groups. to give compoundsof the formula where R, and R are alkyl and R and R are hydrogen. alkylor aryl. The alkyl groups which may be the same or different arepreferably lower alkyl groups e.g. having from 1 to 10 carbon atoms, inparticular those having l to 5 carbon atoms.

Specific examples of compounds of formula (ll) are:

2 2 -peroxy-diprop-2- 1amine Me NH b.p. 40-42C at 12 mun-.Hg.

2 2' -peroxy-dibut-2-ylam fine He NH Me c c Et 00 E III! hp. 66-68% at12 m-m. Hg.

1 ,1 '-peroxy-dibut-1-y1amine NH H C CH CH CH G \IlH CH CH b.p. 50C at0.1 mm. Hg.

As indicated above one of the carbon atoms in the structural unit (I)may form part of a ring into which it is bonded by the free valenciesshown in the structure (l). Examples of such compounds are the compoundscontaining the structural unit s c/ l5 8 9 2 M Rm R14 where R; to R arehydrogen or alkyl groups, R, is alkyl and R is hydrogen. alkyl or aryl.The alkyl group R, and R when an alkyl group, are preferably lower alkylgroups for example those having less than IO. preferably less than 5carbon atoms.

R,-. to R may be hydrogen or alkyl and examples of suitable alkyl groupsare the lower alkyl groups eg those having 1 to 5 carbon atoms inparticular methyl. ethyl and propyl groups although longer alkyl chainsmay be also be used. Examples of compounds of formula (III) are those inwhich at least one of R to R is an alkyl group. in particular at leastone of R; to R is an alkyl group while R,-.. R... R and R are hydrogen.An example of a particularly suitable pattern of substituents is that inwhich R; and R are both methyl. while one of R and R is methyl theremaining R,-. to R being hydrogen.

Both carbon atoms in the structural unit I) may form part of rings intowhich they are bonded by the free valencies shown in the structure (I)and examples of such compounds are those of formula in the ring.Examples of compounds of formula (IV) are those compounds where X is aradical having 4 to 6 carbon atoms in the ring. Examples of suchcompounds are:

R R H 7 R R 19 NH R 7 20 325 R R 29 R R 1 30 (V) 34 55 55 245 R 0% R 46R 2 52 47 37 R R R 4 5 4B R R R 5 49 (v1) 67 68 R 9 R7 R7 R R R 72 60 6175 (VII) where R to R71; are alkyl groups or hydrogen.

The preferred compounds are those in which R to R is hydrogen or loweralkyl, e.g. methyl. ethyl, propyl although the compounds may have longerchains.

Specific examples of compounds according to the present invention are:

l .l '-peroxydicyclopentylamine which is a white solid with a meltingpoint of 22 23C.

4.4' dimethyll l '-peroxydicyclohexylamine which is a white solid withmelting point 1 19 121C.

Me NH Me Q 00 (VI Me Me Me Me 3.3.3 ,3 .5.5'-hexamethyl-l ,l'-peroxydicyclohexylamine with boils at l24 l26C at a pressure of 0.4

mm.Hg.

l.l '-peroxydicycloheptylarnine which boils in the range l30C at apressure of 0.8 mmHg.

U 00 (xxx) Me Me 1,1 '-peroxy-3 3,5-trimethylcyclohexyl cyclopentylaminewhich boils at 92 96C at 0.3 mm.Hg.

(vII') M. NH

Me Me [,1 '-peroxy-3.3.5-trimethylcyclohexylcyclohexyll.l'-peroxydicyclohexylamine which is a white solid insolublein water but soluble in ethanol, which melts at 40 4l .5C and distillsat 94 97C at a pressure (vml of 0.4 mm.Hg. and at l38- I40C at apressure of 12 mm.Hg.

The present invention also includes a process for making compoundshaving the essenetial skeletal structure (I) by reacting together atleast one compound having the essential skeletal structure:

C (IX) with hydrogen peroxide and ammonia.

The free valencies of the carbon atom in the structure (XI) may besatisfied by any group which will be inert under the reaction conditionsi.e. will not enter into reaction with ammonia or hydrogen peroxide.

The carbonyl compound may be acyclic or cyclic. Where the carbonylcompound is acyclic examples of suitable groups which may be bound tothe free valencies are hydrogen and alkyl preferably lower alkyl. It ispreferred that at least one alkyl group is bound to a free valency ofthe carbon atom of structure (IX) the other group being hydrogen oralkyl, to give compounds of formula where R;; is alkyl and R; ishydrogen or alkyl. Preferably alkyl groups are bound to both freevalencies. Specific examples of carbonyl compounds which may be used areacetone, ethyl methyl ketone. and nbutyraldehyde.

The compounds formed by reaction of a compound of formula (X) withhydrogen peroxide and ammonia are those of formula (II) In place ofacyclic carbonyl compounds, at least one compound of formula where X isa divalent aliphatic radical may be used. Carbon atoms may be the onlyatoms in the ring. The cyclic ketone may be for example a ketone withbetween and I2 carbon atoms in the ring, X would then have 4 l l carbonatoms forming part of the ring.

Examples of suitable ketones are those of formulae where R to R arealkyl groups or hydrogen.

The preferred compounds are those where R1 to R are hydrogen or loweralkyl e.g. methyl. ethyl. propyl. but compounds with longer alkyl chainscan also be used. Examples of compounds of the above formulae which maybe used are those in which not more than one alkyl group is joined toeach carbon atom in the ring. Compounds in which two alkyl groups arejoined to a single carbon atom may be used, however. When the ring is a6 carbon atom ring, then any gem-dialkyl groups are preferablysubstituted in positions 3.4 or 5 on the ring.

Examples of ketones which may be used are cyclopentanone,2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone.3.3.S-trimethylcyclohexanone (dihydroisophorone), and cycloheptanone.

The compounds produced by reaction of a compound offormula (XI) withhydrogen peroxide and ammonia are those of formula (IV). Where only onecompound offormula (XI) is used. and the radical X is inert under thereaction conditions the radicals X and X in the compound of formula (IV)will be the same although the compound of formula (IV) may exist in anumber of different stereoisomers.

It is possible that formation of compounds having the structural unit(I) from carbonyl compounds having the structure (IX) by reaction withammonia and hydrogen peroxide proceeds by way of compounds containingthe structural unit OH C (XV) DOE and OH I I m C O0 C and wherecompounds of formula (XV) and (XVI) exist they may be reacted withammonia to give compounds containing the structural unit (I). Thus theformation of compounds containing the structural unit (IV) by reactionsof compounds of formula (XI), hydrogen peroxide and ammonia may proceedby way of compounds of formula A on X C (XVII) and or: OH A I x c 00- cx (XVIII) V where X is a divalent aliphatic radical, and where peroxidesof the above formula can be formed e.g. by oxidation of cyclic alcoholswith molecular oxygen or by reaction of cyclic ketones with hydrogenperoxide. these peroxides may be reacted with ammonia to give compoundsof formula (IV) Thus l,l '-dihydroxydicyclohexyl peroxide OH OH can bereacted with ammonia to give l,l '-peroxydicyclohexylamine.

In the same way the formation of compounds of formula (II) fromcompounds of formula (X), hydrogen peroxide and ammonia may proceed byway of compounds of formula 11o OOH 112 OH OH 114 where Rum. R and Rhave the same meaning as R;,- in formula (X) while Rn", R1 and R havethe same meaning as R in formula (X) and where these exist they may bereacted with ammonia to give compounds of formula (II).

It is possible that the formation of the compounds of formula (IV) fromcompounds of formula (XI), hydrogen peroxide and ammonia may proceed byway of an intermediate of formula which then reacts further. Wherecompounds of formula (XXI) can be isolated they may be reacted withcompounds (IX) to give compounds of formula (I). Thus compoundscontaining the structural unit (I) may be prepared by reacting acompound of formula R OOH 118 (XXII) 119 4 1 R1 3 with a compoundcontaining the structural unit R to R have the same meaning as R,-. to Rin structure (III) and the remarks made concerning R,-, to R inconnection with structure (III) apply also to R to R in the compound offormula (XXII). Before proceeding with the discussion of the reaction of(XXII) and (IX) it will be necessary to discuss the preparation of(XXII). Compounds of structure (XXII) may be prepared by reactingtogether a cyclic ketone of formula with ammonia and hydrogen peroxidewhere R to R have the same meaning as R,-, to R in formula (III) and theremarks made concerning R to R in connection with (III) apply also to Rto R in (XXIII). A particularly preferred compound of formula (XXIII) is3,3,S-trimethylcyclohexanone. as the compound of formula (XXII) namelyI-amino-3,3,S-trimethylcyclohexyl hydroperoxide is readily isolated fromthe reaction mixture before further reaction takes place.

A novel compound of formula (XXII) which may be produced by the processdescribed above is l-amino- 3,3,5-trimethylcyclohexyl hydroperoxide.This compound whose structure was established by nuclear magneticresonance and infra-red spectroscopy, and by elemental analysis isunstable if kept at temperatures much above 0C and melts withdecomposition at 67 675C. The compound may be made by the process of thepresent invention using dihydroisophorone as the cyclic ketone OOH Me 0Me NH Me Me Me XXII Another novel compound which may be made by theprocess of the present invention is l-amino-4- methylcyclohexylhydroperoxide which may be made by the process of the present inventionusing 4-methylcyclohexanone as starting material.

3' 2 2 "H2 Me Me xxrI Other novel compounds of formula (XXII) arel-aminocyclohexylperoxide which has m.p. 57 58C (rapid heating). 47Cwith decomposition (slow Heating), and l-aminocyclododecyl hydroperoxidewhich has m.p. of 72- 73C.

Having discussed the formation of the compounds of formula (XXII) I willreturn to the reaction of these compounds with compounds of formula(IX). The comments made concerning the groups which may be on the freevalencies of the compound containing the structural unit in connectionwith the preparation of compounds containing the structural unit (I)apply also to the reaction of (XXII) and (IX). Thus compounds of formula(X) may be used, to give products of formula (ll) while compounds offormula (XI) give products of formula (IV).

Examples of specific carbonyl compounds which may be used areformaldehyde, acetaldehyde. nbutyraldehyde. acetone, ethyl methylketone. diethylketone. acetophenone, cyclopentanone. cycloheptanone. and3,5.5-trimethylcyclohexanone.

All the reactions described above can be carried out without a catalyst,although catalysts can be used, by bringing the reactants into contact.This may be done by mixing the reactants in the liquid phase. Where thereactants are all liquids or gases as may often be the case whencarbonyl compounds of structure (IX), hy-

drogen peroxide and ammonia are being reacted together, simple mixing ofthe reactants may be sufficient. Where one of the reactants is a solidit may be dissolved in a solvent, which should preferably be misciblewith the other constituents of the reaction mixture. Thus when reactingcarbonyl compounds with hydrogen peroxide and ammonia the solvent usedshould be miscible, preferably completely, with hydrogen peroxide andwater. Even if the reactants are all liquids or gases it may bedesirable to add a solvent to ensure adequate contact between thereactants. Thus when reacting carbonyl compounds, hydrogen peroxide andammonia together it may be desirable to add a liquid which is a solventfor the carbonyl compound and is miscible preferably completely withhydrogen peroxide and water. It may often be convenient to use a solventin which the reactants are soluble and the desired reaction productinsoluble so that the reaction product can be separated from thereaction mixture by filtration. This may be particularly useful whendealing with the less stable products, as the need to carry outdistillations or solvent extractions which can cause considerable lossesof product is thereby avoided. Examples of solvents which may be usedare methanol, ethanol, light petroleum, ether, dioxan.dimethylformamide.

When bringing reactants into contact to carry out the reaction it is notessential that all the reactants should be entirely in the liquid phaseand it may be desirable to mix the reactants together in the presence ofa sol vent for one of the reactants and the reaction product.

Where hydrogen peroxide is a reactant it will generally be in the formof an aqueous solution. The strength of this solution may vary betweenmoderately wide limare those containing between 5- l 00% by weight ofthe total solution of hydrogen peroxide. Thus commercially availablesolutions containing about 28-30% by weight of hydrogen peroxide aresatisfactory. The reaction mixture may contain a hydrogen peroxidestabiliser e.g. sodium ethylene diamine tetraacetate (EDTA). V

The concentration of hydrogen peroxide in the reaction mixture in whichit is used will depend not only on the strength of the hydrogen peroxidesolution added but on the quantities of other reactants and solventspresent. The quantity of hydrogen peroxide in the reaction mixture mayvary over a wide range. Examples of suitable concentrations of hydrogenperoxide in the reaction mixture are those in the range 5-40% by weight,particularly suitable concentrations being those in the range lO-20% byweight.

In the reaction of carbonyl compound (IX) with hydrogen peroxide andammonia the molar ratio of ketone and hydrogen peroxide reacted togethermay vary over a moderately wide range for example between 4:1 and 0.5:lbut when preparing compounds having the structural unit (I) it ispreferred to use at least two moles of ketone for one mole of hydrogenperoxide the stoichiometric ratio being 2:1. When it is desired toprepare compounds of formula (XXII) it is preferred to use a molar ratioof ketone to hydrogen peroxide of about 1 l this being thestoichiometric ratio for the reaction.

Where ammonia is a reactant it may be fed into the reaction mixture inthe form ofa gas or as a solution in for example water. Theconcentration of the ammonia solution may vary over moderately widelimits and 0.880 ammonia i.e. an aqueous solution having a relativedensity of 0.880, is suitable. If desired the reaction may be startedwith the ammonia added to the other reactants as a solution and may becontinued by passing gaseous ammonia into the reaction mixture. Whereammonia is a reactant it is preferred to use a slight excess over thestoichiometric quantity but the quantity of ammonia is not critical.

The temperatures at which the reactions described above may be carriedout will depend upon the thermal stability of the reactants and productsas the use of temperatures sufficiently high to decompose the reactantsand products must be avoided.

When preparing compounds of structure (I) in which the free valencies ofboth carbon atoms do not bond the carbon atoms into a ring eg whenpreparing compounds of formulae: (II) or (III). Examples of temperatureswhich may be used are temperatures in the range -20C to +20C, inparticular l0C to +l0C. When reacting compounds of formula (Xl) withhydrogen peroxide and ammonia or compounds of formula (XVII) or (XVIII)with ammonia it may be possible to use a somewhat wider range oftemperatures, for example temperatures in the range 20C to +C,preferably those in the range 0C to 50C. Temperatures of about 40C areoften particularly suitable. In the preparation of compounds of formula(XXll) and in the reaction of those compounds with compounds (IX) it ispreferred to use temperatures in the range 20C to +20C, for exampletemperatures in the range l0C to +lOC in particular temperatures below0C. The duration of the reaction when preparing compounds containing thestructural unit (I) will depend upon the temperature and the particularreactants used and may varyover a wide range. The reaction may becomplete in 2 to 3 hours but longer times may sometimes be desirable.

When preparing amino-hydroperoxides of formula (XXII) it may benecessary to control the reaction time carefully to prevent the compound(XXII). reacting further. The optimum time for this reaction can bedetermined by the man skilled in the art and may for example range from/2 to 7 hours. The pressure in the reactions described above may varyover a moderately wide range, atmospheric pressure or pressures close toatmospheric pressure generally being most convenient. When carrying outreaction in which ammonia is a reactant pressures below atmosphericpressure will cause a reduction in the ammonia concentration in thereaction system which may lead to reduced yields and it may be desirableto use pressures above atmospheric pressure to obtain a highconcentration of ammonia.

The reactions described above can be carried out batchwise orcontinuously.

The peroxide (l) and (XXII) may be recovered in any suitable manner ormay be used, without recovery, in further reactions. Where the reactionis carried out in aqueous solution the peroxide of formula (I) willgenerally separate out as a solid or in a liquid layer from the aqueoussolution. Where the peroxide (1) is to be reacted further, this productrich in peroxide (1) can be separated from the reaction mixture and usedwithout further purification. Alternatively the peroxide (I) may beextracted from the reaction using a suitable organic solvent e.g.chloroform, ether, light petroleum, benzene. or ethyl acetate. Theperoxide (I) may then be separated from the extract by distillation, ifnecessary under reduced pressure, provided that the distillationtemperature is not so high as to decompose the peroxide. Alternatively,it may be possible to precipitate the peroxide from the extract byaddition of water. lt may also be possible to obtain the solidcrystalline peroxide directly by filtration from the reaction mixture.

The l-amino-hydroperoxides (XXII) will often precipitate from thereaction mixture and can be separated by filtration from the reactants.Where other products are obtained which are insoluble in the reactionmixture it may often be possible to dissolve these other products withhydrophobic solvents e.g. light petroleum.

It should be noted that the compounds according to the present inventionare not restricted to those made from carbonyl compounds (IX) carryinggroups which are inert under the reaction conditions. The groups bondedto the free valencies shown in structure (I) may well differ from thosefound in the compounds from which the compound of structure (I) isprepared. Thus when ammonia and hydrogen peroxide are reacted togetherwith a carbonyl compound which contains groups which react with ammoniaand/or hydrogen peroxide it may often still be possible to obtaincompounds containing the structural unit (I) but the groups bonded tothe free valencies in the structure (I) will not necessarily then be thesame as those bonded to the carbonyl group in the starting material.

The invention will now be illustrated by the following Examples. Theperchloric acid equivalents of substances given in the examples weredetermined by titrating an anhydrous N/lO solution of perchloric acid inacetic acid with a solution in acetic acid of a weighed sample of thesubstance whose equivalent is being determined. The peroxide or activeoxygen equivalents of substances given in the examples were determinedby adding a saturated solution of potassium iodide (containing aquantity of potassium iodide in excess of that required to react withall the peroxide groups in the substance under investigation), to aceticacid to which a small quantity of sodium bicarbonate is added togenerate carbon dioxide. A weighed sample of the substance underinvestigation is then added. the mixture heated on a boiling water bathfor 5 minutes, and then cooled. A little water is then added and themixture titrated with N/ 10 sodium thiosulphate solution.

EXAMPLE 48 Acetone (58 g.), 30% hydrogen peroxide cc) and the sodiumsalt of E.D.T.A. (l.0 g.) were mixed and saturated with gaseous ammoniaat about 0C., and the solution stored overnight at 0C. The solution wasextracted with ether and the ethereal extract dried and evaporated.Distillation of the residue gave a fraction (2l.l g.), b.p. 55C/l2 mm.Hg., which on redistillation gave a product b.p. 40 42C at l2 m.m.Hg.This product on analysis was shown on the basis of elemental analysis,nuclear magnetic resonance. and infra-red spectroscopy to be2,2-peroxy-diprop-Z-ylamine ME NH lie Me 00 MB The peroxide equvalentwas and the perchloric acid equivalent was I47. The elemental analysisgave C, 55.05%; H, l0.l%; N, 10.2%.

EXAMPLE 49 Me Me EXAMPLE 50 A mixture ofn-butyraldehyde (72 g. 30%hydrogen peroxide (70 c.c.), methanol (45 c.c), ammonium acetate (8 g.)and sodium salt of E.D.T.A. l g.) was cooled to about 0C and saturatedwith gaseous ammonia. The solution was stored at 0C overnight andextracted with ether. The ethereal extract was evaporated to leave aresidue (74.5 g.) having a peroxide equivalent of 171. A small portionof this residue was distilled to give a fraction b.p. 50C at 0.1m.m.Hg., with peroxide equivalent of I65 and a perchloric acidequivalent 37 of 188. and elemental analysis C. 60.5%; H. 10.95% and N,8.9%.

This product was identified as 1.l'-peroxy-dibut-lylamine H 11H H C CCHECH CH O CH CH G'H3 EXAMPLE 5 I A mixture of isophorone (41.4 g.).hydrogen peroxide (45.2 c.c.). methanol (350 c.c.), 0.880 ammonia (80c.c.). and sodium salt of E.D.T.A. (1.0 g.) was cooled to temperaturesat or below 0C and saturated with gaseous ammonia, then stored at 0C forseveral days. A solid (0.8 g.) was filtered off. rinsed with coldethanol and refiltered, to give material with m.p. 74 81C. perchloricacid equivalent 179. Elemental analysis gave C. 56.2%; H. 9.2%; N, 7.1%.Spectroscopic evidence showed this to be the l-amino-lhydroperoxide ofepoxyisophorone The filtrate was extracted with ether and the etherealextract evaporated and distilled to give a fraction (27.7 g.) b.p. 54Cat 0.3 mm. Hg; consisting mainly of isophorone epoxide with someisophorone. and a fraction (3.4 g.) b.p. 136 141C at 0.3 mm. Hg, withperchloric acid equivalent of 340 and active oxygen equivalent of 199.Elemental analysis gave C, 69.4%. H. 9.2%, N, 5.3%.

This peroxide Me Me lle Me Me Me was of the type according to thepresent invention and this example illustrates the production ofcompounds according to the present invention from carbonyl compounds inwhich the groups bound to the carbonyl group are not inert.

EXAMPLE 52 l-Amino-3.3.5-trimethylcyclohexyl hydroperoxide (34.6 g.) wasadded with stirring to acetaldehyde (12 g.) in petrol (light petroleumspirit (b.p. 60C))( 60 c.c.) with the temperature kept at below 0C. Whenthe peroxide had dissolved. the aqueous layer was separated. and theorganic phase treated with concentrated sulphuric acid (6 drops) andmagnesium sulphate and left at room temperature. The solution was thenfiltered. washed with water. dried. and distilled. In addition todihydro-isophorone a product (32.0 g.) was obtained which boiled at 78Cat 0.5 mm. Hg. pressure, and had a peroxide equivalent of 221. Elementalanalysis gave C. 66.3%; H. 10.6%; N, 7.0%. This was identified as:

Me H

Me Me EXAMPLE 53 1-Amino-3,3.S-trimethylcyclohexyl hydroperoxide 17.3 g;78% pure) was added with stirring to acetaldehyde (12 g.) in lightpetroleum (b.p. 40 60C) (50 c.c.) with cooling to below 0C. When thehydroperoxide had dissolved. the organic layer was separated, treatedwith solid magnesium sulphate and stored at 0C overnight. The solutionwas then filtered. washed and distilled as in Example 52 and gave, inaddition to dihydroisophorone. the same product 13.0 g.) as Example 52.

EXAMPLE 54 EXAMPLE 55 Butyraldehyde (14.4 g.) was mixed with petrol(b.p. 40 60) (50 c.c.) and to the stirred solution at below 0C was addedl-amino-3.3,S-Irimethylcyclohexyl hydroperoxide 17.3 g.; 89% pure). Theperoxide dissolved within a few minutes. To the solution were addedmagnesium sulphate and concentrated sulphuric acid (6 drops) and themixture stored at 0C overnight. The solution was filtered, the filtratewashed with water. dried and distilled to give unreacted butyraldehyde.dihydroisophorone and a product (1 1.1 g.). b.p. 1 10C/l .0 mm. with aperoxide equivalent of 231. and a perchloric equivalent of 233. Theelemental analysis gave C. 68.6%; H. 1 1.05%; N, 6.6%. The product wasidentified as:

EXAMPLE 56 Butyraldehyde (28.8 g.) in petrol c.c.) was cooled to below0C and with stirring treated with 1-amino-1-hydroperoxy-3.3.S-trimethylcyclohexane (33

1. A COMPOUND OF THE FORMULA
 2. The compound according to claim 1 whichis 2,2''-peroxy-diprop-2-ylamine
 3. The compound according to claim 1which is 2,2''-peroxy-dibut-2-ylamine
 4. The compound according to claim1 which is 1,1''-peroxy-dibut-1-ylamine
 5. A compound of the formula 6.The compound according to claim 5 which is
 7. The compound according toclaim 5 which is
 8. The compound according to claim 5 which is
 9. Thecompound according to claim 5 which is
 10. The compound according toclaim 5 which is
 11. The compound of the formula
 12. The compound of theformula
 13. A compound of the formula:
 14. The compound according toclaim 13 which is 1,1''-peroxydicyclopentylamine
 15. The compoundaccording to claim 13 which is 4,4''-dimethyl-1,1''-peroxydicyclohexylamine
 16. The compound according to claim 13 whichis 1,1''-peroxydicyclohexylamine
 17. The compound according to claim 13which is 1,1''-peroxydicycloheptylamine
 18. The compound according toclaim 13 which is 3,3,3'',3'',5,5''-hexamethyl-1,1''-peroxydicyclohexylamine
 19. The compoundaccording to claim 13 which is 1,1''-peroxy-3,3, 5-trimethylcyclohexylcyclohexylamine.
 20. The compound of the formula
 21. The compound
 22. Aprocess for the production of a compound of claim 1 wherein R2 and R4are hydrogen or alkyl of 1 to 5 carbon atoms which comprises the step ofreacting together at least one compound of the formula R77R78CO withhydrogen peroxide and ammonia wherein R77 is alkyl of 1 to 5 carbonatoms and R78 is hydrogen or alkyl of 1 to 5 carbon atoms.
 23. A processaccording to claim 22 wherein the carbonyl compound having the formulaR77R78CO is acetone, ethyl methyl ketone or n-butyraldehyde.
 24. Aprocess for the production of a compound of claim 13 which comprises thestep of reacting together at least one carbonyl compound of the formula25. The process according to claim 24 for making1,1''-peroxydicyclopentylamine wherein the carbonyl compound iscyclopentanone.
 26. The process according to claim 24 for making4,4''-dimethyl-1,1''-peroxydicyclohexylamine wherein the carbonylcompound is 4-methyl-cyclohexanone.
 27. The process according to claim24 for making 1,1''-peroxydicyclohexylamine wherein the carbonylcompound is cyclohexanone.
 28. The process according to claiM 24 forproducing 1, 1''peroxydicycloheptylamine wherein the carbonyl compoundis cycloheptanone.
 29. A process for the production of a compound ofclaim 13 which comprises the step of reacting a peroxide of the formula30. A process according to claim 29 for producing1,1''-peroxydicyclohexylamine which comprises reacting1,1''-dihydroxydicyclohexyl peroxide with ammonia.
 31. A process for theproduction of a compound of the formula
 32. A process according to claim31 wherein the compound is 1-amino-3,5,5-trimethylcyclohexylhydroperoxide.
 33. A process for the production of a compound of claim 5wherein R16 is hydrogen or alkyl of less than 5 carbon atoms whichcomprises the step of reacting a compound of the formula:
 34. A processaccording to claim 33 wherein the carbonyl compound R77R78CO isacetaldehyde, n-butyraldehyde, acetone, ethyl methyl ketone or diethylketone.
 35. A process according to claim 22 wherein the reactants arereacted together in the liquid phase.
 36. A process according to claim35 wherein the reactants are reacted together dissolved in a solvent.37. The process according to claim 22 wherein the carbonyl compound ofthe formula R77R78CO is dissolved in a solvent which is miscible withwater and hydrogen peroxide.
 38. The process according to claim 36wherein the solvent is methanol, ethanol, light petroleum, ether, dioxanor dimethyl formamide.
 39. The process according to claim 22 wherein themolar ratio of the carbonyl compound of the formula R77R78CO andhydrogen peroxide reacted together is in the range 4:1 to 0.5:1.
 40. Theprocess according to claim 22 wherein the reaction is carried out at atemperature of from -20* to +20*C.
 41. The process according to claim 40in which the reaction is carried out at a temperature of from -10*C to+10*C.
 42. The process according to claim 41 in which the reaction iscarried out at a temperature below 0*C.
 43. The process according toclaim 24 in which the reaction is carried out at a temperature of from-20*C to +60*C.
 44. The process according to claim 43 in which thereaction is carried out at a temperature of from 0* to 50*C.
 45. Aprocess according to claim 31 wherein the reaction is carried out bymixing the reactants together in solution.
 46. The process according toclaim 45 wherein the reaction is carried out at a temperature of from-20* to +20*C.
 47. A compound according to claim 5 wherein R7 and R8 areboth methyl, one of R11 and R12 is methyl and the remaining R5 to R14are hydrogen.
 48. The compound according to claim 13 which is1,1''-peroxy-2, 2''-dimethyl-dicyclohexylamine.
 49. The compoundaccording to claim 13 which is 1,1''-peroxy-3,3''-dimethyl-dicyclohexylamine.
 50. The compound1,1''-peroxy-3,3,5-trimethylcyclohexyl cycloheptylamine.